Polyazo dyestuffs



Patented Mar. 20, 1951 Werner Bossard," Riehen, and Marcel Reding, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm N Drawing; Application October 14, 1948, Serial No. 54,565. In Switzerland May 16, 1945 This application is a continuation-in-part of the original application Serial No. 669,579 of May 14, 1946, now abandoned.

It has been found that valuable new metal- ;jlisable polyazo dyestuffs are obtained by coupling one mol of a tetrazotiz-ed diamino compound of the general formula v -iwherein X stands for CO'or CONH- and the benzene rings A and B may contain still further :substituents usual in azo dyestuiis, except that no hydroxyl groups or substituents convertible thereinto, such as, e. g., alkoxy groups, may be present in ortho position to the diazo groups, in any order of succession, on the one hand, with one mol of a monoazo dyestuff of the general formula wherein the benzene nucleus C may carry still further substituents usual in azo dyestuiis, and, on the other hand, with one mol of 3 -methyl-5- pyrazolone of the formula N=C--OHa HN/ oo H1 (III) the components being selected in such a manner that the final dyestuffs contain, at least one sulfonic acid group.

The same dyestuffs may also be obtained by .coupling diazotised nitro compounds. of the general formula and wherein the above conditions hold with respect to A and B as well as to the hydroxyl group or any substituent convertible thereinto', either with one mol of a copperable resorcinol monoazo dyestufi' corresponding to the above Formula II or with one mol of 3-methyl-5-pyrazolone of the above Formula'III, converting the nitro group into the amino group, di-a zotising the resulting aminoaz'o dyestu'fi and combining the same with 5 Claims. (Cl. 260-159) one mol of the coupling component III or II re- I spectively, thus yielding the unsymmetrical polyvAs diamino or nitro amino compounds corresponding, to the above Formulae I and IV are suitable for instance: mor p-aminobenzoyl-pphenylene-diamine, their sulfonic acids or car- 'boxylic' acids, m-, or p-nitrobenzoyl-p-phenylenediamine, their sulfonic acids or carboxylic acids, 4.'3- or 4.4 -diaminodiphenylurea and their alkyl-substitution products and the like. Although m-pdiamines'give good dyestuffs as regards the bridging member, nonetheless we prefer p.p'-diamines because they generally yield better dyestufis. v I As diazo components of the resorcinol monoazo dyestufi corresponding to the above Formula II may be enumerated for example diazo compounds of the Z-amino-l-hydroxy-benzene series, such as 2-amino-l-hydroxy-benzene, 4- chloro-2-amino-l-hydroxy-benzene, 4-, 5- or 6- methyl-Z-amino-l-hydroxy-benzene, 2-aminolaminohydroxy-benzene-4-sulfonic acid or carboxylic acid, JZ-amino-l-hydroxy benzene 4 suli'onic acid amide, 4- or 6-chloro-2-amino-1-hydroxybenzene-sulfonic acid, 4- or 6-nitro-2-amino-1- hydroxy-benzene-sulfonic acid, 4- or ii-acetylor benzoylamino-2-amino-l-hydroxybenzene-sulfonic acid, 4.4'--dihydroxy-3-amino- 2 benzene-sulfonic acid-anilide-3'-carboxylic acid, 4.4 dihydroxy 3 aminobenzophenone-3'-carboxylic acid and the like.

Dyestuffs from tetrazotised diamines of For- Zinula-Liurther substituted as desired, together with the coupling components according to the invention generally yield coppered dyeings on V to wet conditions.

cellulose fibres with good fastness to light and However, that group of dyestuffs containing no hydroxyl group nor substituentsconvertible thereinto in the ortho position to the'azo groups in the benzene rings A and B yield dyeings.whichpossess in addition good fastness to acidsand to perspiration The new polyazo dyestuffs. have a goodaffinity to natural ,or regeneratedcellulosic fibres, giving yellowish-brown .to reddish-brown dyeings, the

:shades of which are only slightly changed by after-treatment with copper compounds according to anyone ofthe known methods, whereas the lightfastness thereof as well as their fastness properties 1n theimoist state are substantially in'nproveol.

' Y The present invention will'n'o'w be illustrated by the following exlampleawithout being limited thereto. The parts-are'by weight.

Example 1 24.2 parts of 4.4'diamlnodiphenyl urea are tetrazotised with 13.8 parts of sodium nitrite in the presence of 45 parts of hydrochloric acid and then combined in a slightly acetic acid suspension with an aqueous solution of 31 parts of the monoazo dyestuff obtained by coupling diazotised 2-arnino-l-hydroxy-benzene-4-sulfonic acid with resorcinol. As soon as any trace of tetrazodiphenyl urea has disappeared, there is coupled in the presence of sodium bicarbonate with a neutral, aqueous solution of 9.8 parts of 3-methyl- E-pyrazolone. After 12 hours this is filtered and dried. The resulting trisazo dyestuff which is a dark powder dissolves in water with a brown coloration and in concentrated sulfuric acid with an orange-red coloration. It dyes cellulosic fibres in yellow-brown shades which, on aftertreatment with copper compounds, only slightly change, whereas their fastness properties will substantially be improved.

Dyestuffs having similar properties will be obtained, if, instead of the monoazo dyestufi" from diazotised 2-amino '1 hydroxy-benzene-4-sulfonic acid, coupled with resorcinol, there is used a monoazo dyestuif obtainable by coupling resorcinol with diazotised 2-amino-1-hydroxybenzene-4-carboxylic acid, 4-nitro 2 aminol-hydroxy-benzene 6 sulfonic acid, 6-nitro- 2-amino-1-hydroxy-benzene 4 sulfonic acid, 4-chloro 2 amino-l-hydroxy-benzene 6 sulfonic acid, 6 chloro-2-amino-1-hydroxy-benzene-4-sulfonic acid, 4-acetylaminoor 4-benzoylamino-Z-amino-1-hydroxy-benzene 6 sulionic acid, fi-acetylaminoor 6-benzoylamino- 2-amino-1-hydroxy-benzene-4-sulfonic acid.

Example 2 22.7 parts of 1 (4 aminobenzoylamino)- 4-aminobenzene are tetrazotised with 138 parts of sodium nitrite in the conventional manner and coupled in a slightly acetic acid solution with a litmus-acid aqueous solution of 31 parts of the monoazo dyestufi from diazotised 2-amino- 1-hydroxy-benzene-4-sulfonic acid and resorcinol. After several hours the formation of the intermediate product is complete. Then there is first treated with a neutral solution of 9.8 parts of 3-methyl-5-pyrazolone and subsequently 10 parts of sodium bicarbonate in 200 parts of water are gradually added. After completion of the coupling the finished trisazo dyestuff is filtered ofi and dried. It constitutes a dark powder which is soluble in water with a brown coloration and in concentrated sulfuric acid with a yellow-brown coloration and produces on fibres from natural or regenerated cellulose yellowishbrown dyeings, which, on after-treatment with copper compounds in any known manner, possess very good fastness properties.

Dyestuffs with similar properties will be obtained by using instead of the monoazo dyestuff from diazotised 2 amino-l-hydroxy-benzene- 4-sulfonic acid coupled with resorcinol, a monoazo dyestuif obtainable by coupling resorcinol with diazotised 'Z-amino -.E1 hydroxy-benzenel-carboxylic acid, 4-nitro-2-amino-l-hydroxy-benzene-S-sulfonic acid, 6-nitro-2-amino- 1-hydroxy-benzene-4-sulfonic .acid, 4- .chloro- 2 amino-l-hydroxy-benzene 6 sulfonic acid, 6 chloro-Z-amino-l-hydroxy-benzene 4-sulfonic acid, 4-acetylamino or 4-benzoylamino-2eaminol-hydroxy-benzene-fi-sulfonic acid, :6 --a cetyl- 4. aminoor 6-benzoylamino-2-amino-1-hydroxybenzene-4-sulfonic acid.

Example 3 33.? parts of 1 (4 nitrobenzoylamino)- 4-aminobenzene-3-sulfonic acid are diazotised in a conventional manner with 6.9 parts of sodium nitrite and coupled with 9.8 parts of S-methyl- S-pyrazolone in the presence of an excess of sodium carbonate. Then there is heated to 50 C., 12 parts of sodium sulfide in form of a 15% solution are poured thereinto and, after complete reduction, the aminoazo dyestuif precipitated by means of hydrochloric acid is filtered off. Then there is mixed with '7 parts of sodium nitrite and diazotised in the cold by adding quickly 35 parts of concentrated hydrochloric acid. After several hours the diazonium compound, which has been filtered off and suspended in 400 parts of water, is combined in a Weakly acetic acid solution with 30.9 parts of the monoazo dyestuff obtainable by coupling diazotised 2-amino-1-hydroxy-benzene- 4-sulfonic acid amide with resorcinol. The coupling is accelerated by adding dropwise 10 parts of sodium bicarbonate in 200 parts of water. After some standing the finished trisazo-dyestufi is precipitated from an alkaline solution by means of sodium chloride, filtered off and dried. The new dyestuif is a dark powder dissolving in water and in concentrated sulfuric acid with a brown coloration and dyeing cellulosic fibres in yellowbrown shades which, after having been treated with copper sulfate, possess very good fastness properties.

By replacing in the above example the monoazo dyestuif obtainable by coupling diazotised 2 amino-l-hydroxy-benzene 4 sulfonic acid amide with resorcinol by a monoazo dyestuif which is obtainable by coupling resorcinol with diazotised 4-methyl-2-amino-l-hydroxy-benzene, 4-chloro-2-amino-1-hydroXy-benzene or 4-nitro- Z-amino-l-hydroxy-benzene, dyestuffs with similar properties will be obtained.

I Example .4

22.7 parts of 1-(3'-aminobenzoylamino)-4- aminobenzene are tetrazotised with 13.8 parts of sodium nitrite and treated with a litmus-acid solution of 34.5 parts of the monoazo dyestuff from diazotised 6-chloro-2-amino-1-hydroXybenzene-4-sulfonic acid and resorcinol and with 15 parts of sodium acetate. The coupling is maintained slightly acid to litmus by adding dropwise a dilute sodium carbonate solution. As soon as the intermediate product has completely been formed, there is coupled with 9.8 parts of 3- methyl-5-pyrazolone in the presence of sodium bicarbonate. The resulting trisazo dyestuif is filtered 01f after 12 hours and dried. It is a-dark powder dissolving in water and in concentrated sulfuric acid with a yellow-brown coloration. It dyes cotton and fibres from regenerated cellulose in yellow-brown shades which, when aftertreated with copper salts, possess excellent fastness properties.

'Dyestuifs having similar properties can be obtained when using, instead of l-(3'-aminobenzoylamino) -4-aminobenzene the 1-(3'-amino- 4' methyl benzoylamino) -4-aminobenzene, 1- (3-amino-4'-chloro-benzoylamino) 4 aminobenzene, 1-(-4'-aminobenzoylamino)=-2-methyl-4 aminobenzene, 1 (4' aminobenzoylamino) 2'- chloro-4-aminobenzene, 1-- (3f amino-4-methylbenzoylamino) -2-methyl-4-aminobenzene or the 1- (-3 -aminobenzoy-lamino-) 4 .aminobenzene-B- sulfonic acid group and corresponding to the general formula:

disulfonic acid and, instead of the monoazo dye- 10 wherein X represents a member selected from stuff from diazotised 6-chloro-2-amino-1-hydroxy-benzene-4-sulfonic acid and resorcinol, any other resorcinol-monoazo dyestuff mentioned in Example 1.

the group consisting of CO and NH.CO, and ZN=N represents the radical of a diazotized ohydroxyarylamine of the benzene series.

2. A polyazo dyestuif corresponding to the In the following table further dyestuffs which 15 formula SOaH being shown in the first column and the coupling 3. A polyazo dyestufi? corresponding to the formula 4. A polyazo dyestuff corresponding to the component II being enumerated in the second formula:

0H Cl N=N -N=NC ONHC N=NCH(|3CH;

HO OH 1 N aH A column. As coupling component III there is always used 3-methyl-5-pyrazolone.

Shade of the coppertetrazo compound frommonoazo dyestufi from resorcinol and diazotized containing dyeing on cellulosic fibres 1-(3;ami.uobenzoylamino)-4-amino-benzene-3-sulfonic 2-amino-l-hydroxy-benzene-4-sulfonic acid amide. yellowish-brown. 1-?f -a mi.nobenzoylamino)-4-amino-benzene-3-sulfonic do Do. l-gikaanligobenzoylamino)-4-amino-benzene-8-carbox- 2-amino-l-hydroxy-benzene-i-sulfonic acid Do. 1-(4-aminobenzoylamino)-4-aminobenzene 4. ic-iddi-hydroxy-3-aminobenzophenone-3carboxylic Do. 4.4'-diaminodiphenyl-ureo-3.3-dicarboxylic acid Z-anaifno-1-hydroxy-benzene-i-sulfonic acid yelloggbrown.

4.3-diaminodiphenyl-urea What we claim is: 1. A polyazo dyestufi containing at least one REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,155,001 Schmid Apr. 18, 1939 2,191,800 Murphy et a1. Feb. 27, 1940 2,241,796 Taube et a1. May 13, 1941 5. A polyazo dyestufi corresponding to the formula WERNER BOSSARD. MARCEL REDING.

Number Name Date 2,404,198 Straub et al. July 16, 1946 2,428,130 Straub et a1 Sept. 30, 1947 2,459,467 Straub et a1 Jan. 18, 1949 

4. A POLYAZO DYESTUFF CORRESPONDING TO THE FORMULA: 